Polymeric tri-beta-hydroxyethyl cyanurate



Patented June 19 l i POLYMERIC TRI-fl-HYDROXYETHYL CYANURATE Pierrepont Adams, Glenbrook, Conm, assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application January 10, 1947,

Serial No. 721,464

4 Claim,

This invention relates to a new and improved method of preparing a resinous composition, and more particularly to the method of preparing a resinous composition which comprises heating tri-p-hydroxyethyl cyanurate at a temperature between 105 C. and 150 C. to form a resinous condensation product thereof. Specifically, the invention is concerned with the preparation of a resinous composition by heating trip-hydroxyethyl cyanurate while admixed with a condensation catalyst within the aforementioned temperature range until a resinous condensation product of the said cyanurate has been obtained. Examples of condensation catalysts that can be used are sodium hydroxide and phosphoric acid.

It was known prior to my invention that trimethyl cyanurate could be transesterified with a monohydric alcohol. Thus, Hofmann [Ber. 19, 2061-2083 (1886)] observed that if trimethyl cyanurate be refluxed with an equivalent-amount of sodium ethoxide in ethanol, it is completely transformed to the triethyl ester. However, to the best of my knowledge and belief it was not known that resinous compositions could be prepared from tri-p-hydroxyethyl cyanurate as briefly described in the first paragraph of this specification and more fully hereinafter.

In order that those skilled in the art better may understand how the present invention may be carried into efiect, the following examples are given by way of illustration and not by way of limitation. All parts are by weight unless otherwise stated.

EXAIVIPLE 1 Preparation of tri-fl-hydroryethyl cyanurate To 450 parts of ethylene glycol there was added about 9.5 parts of methanol, in which 0.5 part of sodium metal had been dissolved, and 102.6 parts of trimethyl cyanurate. The reaction mixture was heated by means of an oil bath maintained at 100-110 C. for two hours under a pressure of 65-85 mm. At the end of this time 62 parts of methanol had distilled from the reaction mass. To the reaction mass there was added 8.75 parts by volume of hydrochloric acid to neutralize the catalyst, and the excess glycol (285 parts) was distilled at 60 C. at 1-2 mm. pressure. The viscous residue was dissolved in a small quantity of dioxane, and crude trifi-hydroxyethyl cyanurate crystallized from this solution upon cooling. After recrystallization from hot dioxane, the yield of product was '74 parts, that is, 47% of the theoretical amount of tri-fl-hydroxyethyl 'cyanurate, and the yield was increased to 69% of the theoretical by working up the filtrates. A sample which was recrystalformed.

lized several times from hot dioxane melted at l30-132 C., and showed the following analysis:

Per Cent Per Cent Per Cent O H N Calculated for C|HnN|Oa g 6. 76 -16. 09 5. 16. 02 Fmnd 41. 40 5. 70 16.21

Trimethyl cyanurate is prepared, for example, by adding 307 parts of cyanuric chloride to an agitated mixture of 503 parts of anhydrous sodium carbonate and about 1980 parts of methyl alcohol. The addition requires about hour, and the temperature of the reaction mixture is maintained at 25 to 35 C. during this time by means of an ice bath. The mixture is stirred for 5 hours and allowed to stand for about 16 hours. The reaction mass is filtered after it has been heated to boiling, and the resulting salt cake 'is washed with methanol. The methanol is distilled from the solution and the crude product comprising trimethyl cyanurate is crystallized from a 15% aqueous solution of ethylene glycol monoethyl ether. A second crop of crystals is obtained by concentrating the mother liquor to a volume of 600 parts. The total yield of trimethyl cyanurate, melting at 134-134.5 C., is 98% of the theoretical. l I

EXAMPLEZ A sample of tri-fi-hydroxethyl cyanurate was heated in a C. oven for about 65 hours. A hard, water-insoluble resinous material was EXAMPLE 3 Sample N 0.

i??? Catalyst None.

None.

Sodium carbonate. Sodium hydroxide. Phosphoric acid. Sulfuric acid.

Afterheating for 19' hours Sample No. 1 was an opaque solid. The others'formed clear solids. Sample No. 5 was slightly yellow incolor, while No. 6 was brown. All were hard and brittle resins.

The procedure was repeated but in this case the samples were dried for 30 minutes at 105 C. and then were heated at 150 C. Only one sample containing no catalyst was prepared. After 19 continuing the distillation for another minutes, the yield of product amounted to 740 parts. The product was hydrophobic ina large excess of water.

hours heating at 150 C. the sample containing 5 no catalyst and the one containing the phosphoric m 8 acid catalyst were slightly yellow in color. while the sample containing the sulfuric acid was A ff, brown. All samples formed hard and brittle R resinous condensation products.

mm 4 iiifiifiil fioiifffxxi:::::::::::::::::::::::: i A mixture or 100 parts of trl B hs drouethYl Sodium (d ssolvedinaboutIilJpartsofmelhunol). 2 gi'gg zi f g g flag :5 3 2 2:3 3 u Essentially the same procedure was followed as until a solution was obtained which remained g d under Example Alter distilling for minutes a water-soluble transesteriilcation clear on cooling. Alpha-cellulose paper was M t ml to 535 ts btamed dipped in this solution to impregnate the paper, g ggfi PM was 0 and then was hung up to air dry. The dried en was continued for another 5 paper was cut into six 64mm x (Much sheets minutes the yield of the product was 520 parts. A hard, r181 d laminated article was produced by and it was hydrophobic in a large excess of water. heating the superimposed sheets for minutes EXAMPLE 9 at 145-160 C. under a pressure of 5000 pounds per square inch. Afipflirx.

ExAMPLs: 5 25 nfiao A ML Trlmethylcyanurate 342 1.0 PM 313; 5% u fii zlfigo ilk'ifiEBhl'ifibBlliEiiiEiiiiJiii ..'f"..

. 3 Trimethylcyanurate 342 1.0 o The procedure followed was essentially the ggm zg gikfi' fi'gfiam'gfi'iiifa'hiiif 186 same as that described under Example 6. A cool) water-soluble transesterification product in a yield amounting to 575 parts was obtained after The mixture of t above i i t was 35 15 minutes distillation. After distilling for an heated under the vacuum produced by a water additional 15 minutes, 545 parts of product was pump in a reaction vessel placed in a 100-110 C. Obtained- It was y p b in 8 '8 excess oil bath. After heating for 30 minutes the resultof W ing transesteriflcation product, which amounted MP 10 to 425 parts, was insoluble in water, alcohol and 4 other organic solvents. Approx Substantially the same results were obtained Parts Molar when only half as much metallic sodium dissolved Ram in about 31.! parts of methanol was used as a Trimeth 1 m 1 o l catals tior th r ct on- Ethy1.n' g 1;iifi. 13330 a mm 6 Sodium( resolved in about 11 partsof methsnol) 0.7

A m The mixture of the above ingredients was Pam 38 heated and stirred in a vessel placed in a 100 Ratio C. oil bath for 30 minutes, yielding a clear solution. The reaction mass was then heated at Efiifiiifiiififfi::::::::::::::::::::::::::: 3% the same temperature under the mum Sodium (dissolvedinaboutSIJpax-tsofmethanol). 2 duced y a Water P p- After 415 mmuteS vacuum distillation the yield of transesteriflca- The same procedure was followed as described Product amwPted 210 Parts- After under Example 5 with the exception that the tilling for an additional 15 minutes, the yield reaction mass was heated in a C. on bath of product was 205.5 parts. It was hydrophobic The resulting transesterification product was in large excess of waterwater-soluble. The yield amounted to 585 parts. Exnn,

When a 21% aqueous solution of this trans- 80 v LE 11 esterification product was heated for 30 minutes Cotton Percale was immersed in 8 bilth 0011- at C. it yielded a resinous film which was 515mg a 10% News Solution of 'fi' insoluble in cold water but was softened by the droxyethyl cyamu'flte and S ium arbonate water. :8 a gstanlnylslhte'lhe gseated cloth was then 35 ea or u s at 0 F. to dry it and EXAM? 7 to form a resinous condensation product of the Same formula as in Example 5 with the extri-fl-hydroxyethyl cyanurate in situ. The dried ception that 2 parts of sodium dissolved in about cloth contained 7% by weight thereof of resin 31.7 parts of methanol was used. The mixture solids. The resin-coated and -impregnated was heated and stirred in a vessel placed in a 7 cloth was washed for 1 hour at F. using 100 C. oil bath for 10 minutes to yield a clear an aqueous SolutiOn containing 54% each f 50 9 solution. It was then distilled at approximately and soda ash, after which it was rinsed in clear the same temperature for 5 minutes under the water at 160 F. The washed and dried cloth vacuum of a water pump, yielding 500 parts of a contained about 4.8% of resin solids, based on water-soluble transesteriflcation product. Upon 75 the weight of the untreated cloth.

Similar results were obtained when the trans-' EXAMPLE 12 Rayon challis was immersed in a bath consisting of a 15% aqueous solutionpi the transesterification product of Example 10 and 0.75% sodium carbonate as a curing catalyst. After heating for 30 minutes at 350 F. the treated rayon showed better abrasion resistance than the untreated rayon;

The resinous and other synthetic materials of this invention may be employed as modifiers, more particularly as plasticizers, of other synthetic resins, in order to impart toughness or improved plasticity and postformability to resins which otherwise are excessively brittle or have poor plasticity. They may be co-reacted with various aldehyde-reaction products, for instance, partial reaction products of an aldehyde, e. g., formaldehyde, and phenol or a substituted phenol, urea or a substituted urea, melamine or other aminotriazine, etc. They also may be incorporated into alkyd resins. For example, the reaction between the polyhydric alcohol and the cyanuric triester may be effected in the presence of an excess of the former, and the unreacted polyhydric alcohol then may be esterifled with phthalic anhydride, maleic anhydride, fumaric acid or other polycarboxylic acid or anhydride in the presence of the transesterification product thereby to obtain a modified alkyd resin. Or, alternatively, the cyanuric triester may be re-esterified using monoglycerides of mono or dibasic acids, e. g., linoleic diglyceride, phthalic diglyceride, etc. 3

toluene, 'butanol, methyl ethyl ketone, amyl acetate, etc., to form coating and impregnating compositions of any desired viscosity. Such compositions may have incorporated therein linseed oil. tung oil, soya bean oil or acids thereof, or other drying or semi-drying oils or acids, as well as driers, more particularly metallic driers, e. g., cobalt naphthenate, manganese naphthenate, cobalt resinate, etc., to improve the adhesive and drying characteristics of the composition.

In the copending application of Edward L..

, ethyl cyanurate at a temperature between 105 The resinous or potentially resinous materials melamine-aldehyde resins, alkyd resins, cellulose esters, cellulose ethers, hydrocarbon-substituted polysiloxane resins, etc. The soluble materials may be dissolved in naphtha, xylene, benzene,

C. and 150 C. to form a resinous condensation product thereof.

2. The method of preparing a, resinous composition which comprises heating tri-p-hydroxyethyl cyanurate admixed with a condensation catalyst therefor at a temperature between C. and C. until a resinous condensation product of tri-fl-hydroxyethyl cyanurate has been obtained.

3. A method as in claim 2 wherein the condensation catalyst is sodium hydroxide.

4. A method as in claim 2 wherein the condensation catalyst is phosphoric acid.

. PIERREPON'I ADAMS.

REFERENCES CITED The following references are of record in the file of this patent? UNITED STATES PATENTS Number Name Date 2,275,467 Pollack et al. Mar. 10, 1942 2,296,823 Pollack et al. Sept. 22, 1942 2,306,440 Hentrich et al Dec. 29, 1942 2,381,121 Ericks Aug. 7, 1945 2,481,156 Schaefer Sept. 6, 1949 2,496,097 Kropa Jan. 31, 1950 Certificate of Correction Patent No. 2,557,625 June 19, 1951 PIERREPONT ADAMS It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 42, for carbonate,, read carbonate,; column 3, Example 5, cglumn 1 thereof, line 3, for part read 'pa rts; column 4, line 2, for 740 rea 4'70;

and that the said Letters Patent should be read as corrected above, so that the same'may conform to the record of the case in the Patent Oflice.

Signed and sealed this 23rd day of October, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. THE METHOD OF PREPARING A RESINOUS COMPOSITION WHICH COMPRISES HEATING TRI-B-HYDROXYETHYL PYANURATE AT A TEMPERATURE BETWEEN 105* C. AND 150*C. TO FORM A RESINOUS CONDENSATION PRODUCT THEREOF. 